HYDROGENATION OF DIENALS WITH RHODIUM COMPLEXES UNDER CARBON MONOXIDE FREE ATMOSPHERE

Description

Technical field

[0001] The present invention relates to the field of catalytic hydrogenation and, more particularly, to the use of a catalytic system comprising a specific rhodium complex in hydrogenation processes for the reduction of a conjugated dienal into the corresponding deconjugated enal.

Prior Art

[0002] The direct selective α-β hydrogenation, i.e. of a specific C=C bond, of a conjugated dienal (α,γ-dienal) is a challenging target. Indeed, the hydrogenation may take place at three different sites (two C=C and one C=O). Moreover, in order to render such process attracting for an industrial purpose, it is preferable to achieve the hydrogenation with an acceptable conversion and with a reasonable turn-over (complex load and reaction time).

[0003] In the prior art, it is possible to find a number of examples of selective α-β hydrogenation of conjugated enals, in particular of geranial/neral, into the respective aldehydes. One may cite Dang T.G et al. in J. of Mol. Catalysis, 1982, 16, 51, wherein geranial is reduced into the aldehyde citronellal. Other similar references are US 4237072 (example 1) or Helv. Chem. Acta, 2001, 230 (footnote 4).

[0004] Trost et al. (in Comprehensive Organic Chem., 1991, vol 8, p. 535) report the reduction of a conjugated enone into a ketone, using conditions which do not work with enal as even mentioned by the author.

[0005] However said documents show that long reaction times are required to perform such simple selectivity with acceptable yields, e.g. from 4 to 24 hours. Furthermore, such references are totally silent on the possibility to apply such systems on the selective α-β hydrogenation of a conjugated dienal as substrate.

[0006] Only one example of selective α-β hydrogenation of a conjugated diene system is reported in the literature (see Burk M.J. et al in J. Am. Chem. Soc., 1998, 120, 657). In this document, it is performed an α-β hydrogenation of a α,γ-dienamide ester, but it is specified that the acetamido group of the substrate is essential to ensure a high selectivity (or enhance reactivity of the targeted C=C double bond). Therefore said document cannot assist the person skilled in the art to conceive the present invention.

[0007] Ojima et al. (in Organomet. 1982, 1390) report the reduction of a conjugated dienone, using a rhodium, complex and a silane as reducing agent, but the product obtained being an allyl alcohol or a deconjugated ketone depending on the nature of silane reagent.

[0008] None of the prior art documents reports the use of the specific catalytic system of the present invention, in particular the use of a base.

[0009] Therefore there is still a need for a process allowing the selective α-β hydrogenation of a α,γ-dienal, and if possible within reaction conditions which are applicable industrially.

Description of the invention

[0010] In order to overcome the problems aforementioned, the present invention relates to processes for the reduction by hydrogenation, i.e. using molecular H₂, of a C₆-C₂₀ conjugated dienal into the corresponding deconjugated enal, characterized in that said process is carried out in the presence of a catalytic system comprising at least a base and at least one complex in the form of a rhodium complex comprising a C₃₄-C₆₀ bidentate diphosphine ligand (L2) coordinating the rhodium.

[0011] According to a particular embodiment of the invention, the conjugated dienal is of formula

wherein, when taken separately, each of R¹, R², R³, R⁴ and R⁵ represents, independently of each other, a hydrogen atom, a phenyl group optionally substituted or a C_1-8 alkyl, alkenyl, cycloalkyl or cycloalkenyl group optionally substituted, provided that at least one of said R¹, R², R³, R⁴ and R is not a hydrogen atom; R¹ and R² or R² and R³ or R³ and R⁴, when taken together, represent a C_3-4 alkadienyl or alkenediyl group optionally substituted; R¹ and R³ or R² and R⁵, when taken together, represent a C_2-3 alkadienyl or alkenediyl group optionally substituted; R⁴ and R⁵, when taken together, represent a C_4-5 alkadienyl or alkenediyl group optionally substituted;
into a deconjugated enal of formula

wherein R¹ to R⁵ are defined as in formula (I);
said process being carried out in the presence of a catalytic system comprising:

• at least a base; and
• at least one Rh(I) complex obtainable by reacting a suitable Rh(I) precursor and a C₃₄-C₆₀ bidentate diphosphine ligand (L2) having a natural bite-angle comprised between 93° and 130°.

[0012] By the expression "natural bite-angle" it is understood the usual meaning in the art, e.g. as defined in P. W. N. M. van Leeuwen, P. C. J. Kamer, J. N. H. Reek, P. Dierkes, Chem. Rev. 2000, 2741.

[0013] Possible substituents of R¹ to R⁵ are one phenyl group or one, two or three COOR⁷, OR⁶ or R⁷ groups, in which R⁶ is a hydrogen atom or a R⁷ group, R⁷ representing a C_1-4 linear or branched alkyl or alkenyl group. According to any one of the embodiments of the invention, only one or two of said R¹ to R⁵ are optionally substituted.

[0014] It is understood that said compounds (II) can be in a racemic or optically active form, depending on the nature of the substrate and on the complex used.

[0015] It is understood that by "alkenyl", "cycloalkenyl" or "alkenediyl" group it is meant here the usual meaning in the art, which is an unsaturated group wherein the unsaturation cannot be conjugated to the carbon-carbon double bonds of the conjugated dienal.

[0016] It is understood that by "conjugated dienal" it is meant a compound possessing at least two carbon-carbon double bonds and an aldehyde functional group, the three of them being conjugated, as indicated in formula (I). The term "conjugated dienal" is therefore understood as optionally comprising also compounds having additional non-aromatic carbon-carbon double bonds provided that said additional carbon-carbon double bonds are not conjugated to the ones of the dienal system.

[0017] It is understood that by "deconjugated enal" it is meant a compound possessing at least one γ-δ carbon-carbon double bond and an aldehyde functional group, as indicated in formula (II). The term "deconjugated enal" is therefore understood as optionally comprising also compounds having additional carbon-carbon double bonds provided that said additional non-aromatic carbon-carbon double bonds are not conjugated to the one of the enal system.

[0018] According to an embodiment of the invention, the compounds of formula (I) and (II) is a C₆-C₁₅ compound, and in particular one may cite those wherein, when taken separately, each of R¹, R², R³, R⁴ and R⁵ represents, independently of each other, a hydrogen atom, a phenyl group optionally substituted or a C_1-4 alkyl or cycloalkyl group optionally substituted, provided that at least one of said R¹, R², R³, R⁴ and R⁵ is not a hydrogen atom; R³ and R⁴, when taken together, represent a C_3-4 alkadienyl group optionally substituted; R⁴ and R⁵, when taken together, represent a C_4-5 alkadienyl group optionally substituted.

[0019] According to any one of the above embodiments, when taken separately, said R¹ represents a hydrogen atom.

[0020] According to any one of the above embodiments, when taken separately, said R² represents a hydrogen atom.

[0021] According to any one of the above embodiments, when taken separately, said R³ represents a hydrogen atom or a methyl or ethyl group or a phenyl group optionally substituted.

[0022] According to any one of the above embodiments, when taken separately, said R⁴ represents a hydrogen atom or a methyl or ethyl group or a cyclohexyl or cyclopentyl group or a phenyl group optionally substituted.

[0023] According to any one of the above embodiments, when taken separately, said R⁵ represents a hydrogen atom or a methyl or ethyl group or a cyclohexyl or cyclopentyl group or a phenyl group optionally substituted.

[0024] According to any one of the above embodiments, when taken together, said R³ and R⁴, when taken together, represent a C₄ alkadienyl group optionally substituted.

[0025] According to any one of the above embodiments, when taken together, said R⁴ and R⁵, when taken together, represent a C₅ alkadienyl group optionally substituted.

[0026] According to any one of the above embodiments, the substrate of formula (I) is one wherein R¹, R² represent each a hydrogen atom, R³, R⁴, R⁵ represent each a hydrogen atom or a methyl or ethyl group or a cyclohexyl or phenyl group optionally substituted, provided that at least one of said R¹, R², R³, R⁴ and R⁵ is not a hydrogen atom; R³ and R⁴, when taken together, represent a C₄ alkadienyl group optionally substituted.

[0027] According to any one of the above embodiments, the substrate of formula (I) is one wherein at least one or two of said R¹, R², R³, R⁴ and R⁵ is a hydrogen atom.

[0028] According to any one of the above embodiments, the substrate of formula (I) is one wherein two or three of said R¹, R², R³, R⁴ and R⁵ are a hydrogen atom.

[0029] According to any one of the above embodiments, the substituents of said R¹ to R⁵ are one phenyl group or one or two OR⁶ or R⁷ groups, in which R⁶ is a hydrogen atom or a R⁷ group, R⁷ representing a C_1-4 linear or branched alkyl group. Preferably said substituents are a OR⁷ or R⁷ group. According to any one of the embodiments of the invention, only one or two of said R¹ to R⁵ are optionally substituted.

[0030] According to a further embodiment of the invention, the substrate is a conjugated dienal that will provide a deconjugated enal that is useful in the pharmaceutical, agrochemical or perfumery industry as final product or as an intermediate. Particularly preferred substrate is a conjugated dienal that will provide a deconjugated enal which is useful in the perfumery industry as final product or as an intermediate.

[0031] Non-limiting examples of substrates are the following: (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal, (2E,4E)-5-phenylpenta-2,4-dienal, (2E,4E)-5-phenylhexa-2,4-dienal, (2E,4E)-4-methyl-5-phenylpenta-2,4-dienal, (2E,4E)-2-methyl-5-phenylpenta-2,4-dienal, (2E,4Z)-4-phenylhexa-2,4-dienal, (E)-3-(4-(tert-butyl)cyclohex-1-en-1-yl)acrylaldehyde, (E)-5-cyclohexyl-4-methylpent-4-enal or (E)-5-cyclohexyl-2,4-dimethylpent-4-enal.

[0032] According to a particular aspect of any one of the invention's embodiments, the invention's process is also characterized by providing compound (II) with a selectivity above 40%, preferably above 60, more preferably above 80%.

[0033] According to a particular aspect of any one of the invention's embodiments, the invention's process is also characterized by providing compound (II) with a conversion of the staring compound of above 60%, preferably above 70%.

[0034] Wherein by "deconjugated enal" it is meant the compound (II), by "aldehyde" it is meant the compound (I) wherein both carbon-carbon double bonds have been reduced and by "alcohol" it is meant the aldehyde wherein the carbonyl has also been reduced.

[0035] The hydrogenation reaction can be carried out in the presence or absence of a solvent. In a particular embodiment of the invention, the process is carried out in the presence of a solvent (in general for practical reasons), and any solvent current in hydrogenation reactions can be used for the purposes of the invention. Non-limiting examples include C_6-10 aromatic solvents such as toluene or xylene, C_1-2 halogenated hydrocarbon such as CH₂Cl₂, C_5-8 hydrocarbon solvents such as hexane or cyclohexane, C_4-9 ethers such as tetrahydrofuran or MTBE, C_3-9 esters such as ethyl or methyl acetate, C_3-6 ketones such as acetone, polar solvents such as C_1-5 primary or secondary alcohols such as isopropanol or ethanol, or mixtures thereof. The choice of the solvent is a function of the nature of the substrate, of the base and of the complex and the person skilled in the art is well able to select the most convenient solvent in each case to optimize the hydrogenation reaction.

[0036] In the hydrogenation process of the invention, the reaction can be carried out under an atmosphere of pure H₂ or under a mixture of hydrogen and of at least an inert gas, such as N₂ or Ar. Preferably, the atmosphere of the reaction medium is CO-free, e.g. the amount of CO present is below 1 ppm. It is understood that in any case the reaction medium is preferably supplied with at least a steochiometric amount of H₂ relative to the substrate ; if less than a steochiometric amount of H₂ then it is achieved only a partial conversion of the substrate. In any case, as non-limiting example, one may cite typical H₂ pressure comprised between 10⁵ Pa and 80 x 10⁵ Pa (1 to 80 bars) or even more if desired. Again, a person skilled in the art is well able to adjust the pressure as a function of the complex load and of the dilution of the substrate in the solvent. As examples, one can cite typical pressures of 3 to 50 x 10⁵ Pa (3 to 50 bar), or even of 5 to 20 x 10⁵ Pa (5 to 20 bar).

[0037] The temperature at which the hydrogenation can be carried out is comprised between 0°C and 100°C, preferably in the range of between 10°C and 80°C. Of course, a person skilled in the art is also able to select the preferred temperature as a function of the melting and boiling point of the starting and final products as well as the desired time of reaction or conversion.

[0038] As mentioned above, the present invention requires the use of a particular catalytic system comprising at least a base and at least a Rh complex. The base and the Rh complex can be premixed, under hydrogen or inert atmosphere, prior to the use of the catalytic system in the process, or they can be added separately into the reaction medium.

[0039] Said base can be any organic or inorganic base having preferentially a pK_a (of the protonated base) comprised between about 2 and 12, in particular between about 2.5 and 12, or even between about 2.8 and 10.5. It is understood that herein by "pKa" it is meant the usual meaning in the art, e.g. the constant measured in water under standard conditions as for example reported in http://www.chem.wisc.edu/areas/reich/pkatable/index.htm.

[0040] According to any one of the above embodiments, said base is : as inorganic base an alkaline or C_4-16 ammonium carbonate or bicarbonate, a basic alox, a siliconate (i.e. silicium derivatives having SiO^- or SiRO^- groups), or an alkaline alkaline-earth or C_4-16 ammonium fluoride; as organic base an alkaline or C_4-16 ammonium C_2-10 carboxylate, or an alkaline or C_4-16 ammonium C_6-10 phenolate optionally substituted, an alkaline or C_4-16 ammonium C_5-15 1,3-diketonate, or a C_8-10 bicyclic amidine.

[0041] According to any one of the above embodiments, said base is a carbonate, or a fluoride, or a carboxylate such as an acetate or benzoate, or a C_5-15 1,3-diketonate such as an acetylacetonate or a 5-oxohept-3-en-3-olate, or phenolate such as a phenolate or a naphtholate.

[0042] According to any one of the above embodiments, said base is sodium acetate, potassium acetate, sodium benzoate, potassium benzoate, sodium (Z)-4-oxopent-2-en-2-olate, sodium (Z)-2,2,6,6-tetramethyl-5-oxohept-3-en-3-olate, sodium phenolate, sodium 2,6-di-tert-butyl-4-methylphenolate, cesium carbonate.

[0043] According to any one of the above embodiments, said base is a potassium salt.

[0044] According to any one of the above embodiments, the Rh(I) complex is a compound obtainable by reacting together:

• a C₃₄-C₆₀ bidentate diphosphine ligand (L2) having a natural bite-angle comprised between 93° and 130°; and
• a suitable Rh(I) precursor of formula
  
          [Rh(L)(S)_vY_r](Y)_1-r     (1)
  
  or
  
          [Rh(L)₂](Y)     (1')
  
  

  wherein r is 0 or 1, v is 0, 1 or 2;

  L represents a C_5-14 hydrocarbon diene;

  S represents a coordinated molecule of a polar organic solvent or water; and

  Y represents a mono-anion.

[0045] The precursor of formula (1) or (1') can be in a monomeric, dimeric or oligomeric form.

[0046] The preparation of the Rh(I) complex is preferably carried out in the presence a solvent. In a particular embodiment of the invention, said solvent is the same optionally used in the hydrogenation process. However other solvents can be used, and as non limiting examples one may cite C_6-10 aromatic solvents such as toluene or xylene, C_5-8 hydrocarbon solvents such as hexane or cyclohexane, C_4-9 ethers such as tetrahydrofuran or MTBE, polar solvents such as C_1-5 primary or secondary alcohols such as isopropanol or ethanol, dichloromethane, water or mixtures thereof. The choice of the solvent is a function of the nature of the substrate, of the base and of the complex and the person skilled in the art is well able to select the most convenient solvent in each case to optimize the hydrogenation reaction.

[0047] The preparation of the Rh(I) complex can be carried out under an inert, or an essentially carbon monoxide and oxygen free atmosphere, e.g. the amount of CO and O₂ present is below 1 ppm. A person skilled in the art knows what is meant by an inert atmosphere. Non-limiting examples of such atmosphere are a nitrogen or argon atmosphere.

[0048] In the preparation of the Rh(I) complex, the temperature of the process can be comprised between 0°C and 100°C, preferably in the range of between 10°C and 60°C. Of course, a person skilled in the art is also able to select the preferred temperature as a function of the melting and boiling point of the starting and final products as well as the desired time of reaction or conversion.

[0049] According to a particular embodiment of the invention, said S is the solvent used as process solvent, including water. According to a particular embodiment of the invention, said S is water or an organic solvent having a dielectric constant ε comprised between about 5 and 40, said constant being measured at standard conditions. Said constant can be retrieved in chemical Handbooks such as "Handbook of Chemistry and Physics", 87th edition, 2006-2007, page 15-13 to 15-23, ISBN 978-0-8493-0487-3, or such as March's "Advanced Organic Chemistry" 5th edition, ISBN 0-471-58589-0, or any other similar reference.

[0050] As typical, non-limiting examples one may cite the following examples of S : a C_4-7 ether (such as tetrahydrofurane (THF) or methyl tertbutyl ether (MTBE)), or a C_1-4 alcohol (such as ethanol or isopropanol), or water or N,N-dimethylformamide (DMF).

[0051] According to a particular embodiment, it is believed that the Rh(I) complex can be described as having the formula

        [Rh(L2)(L)](Y)     (2)

wherein L2, L and Y have the same meaning as for formula (1).

[0052] According to any one of the above embodiments, said diene L represents a linear or branched C₅-C₁₄ hydrocarbon compound comprising two carbon-carbon double bonds or a cyclic C₇-C₁₄ hydrocarbon compound comprising two carbon-carbon double bonds.

[0053] According to a particular embodiment of the invention, said L is a C₇-C₁₂, or a C₇-C₁₀, hydrocarbon compound comprising two carbon-carbon double bonds, optionally substituted, e.g. a cyclic C₇-C₁₂, or a linear or branched C₇-C₁₀, hydrocarbon compound comprising two carbon-carbon double bonds. As well understood by a person skilled in the art, by "cyclic hydrocarbon" it is understood a group comprising a cyclic moiety.

[0054] As non-limiting examples of suitable L, one may cite compounds such as COD (cycloocta-1,5-diene) or NBD (norbornadiene), 2,4-dimethyl-1,3-pentadiene or yet cyclohepta-1,4-diene.

[0055] The examples of L provided above are applicable for both compounds (1) and (2). Anyhow, as a person skilled in the art would recognise, the diene present in the precursor (1) or (1') will be the same as that of the compound (2).

[0056] According to any one of the above embodiments, said Y represents a halide, a C_5-15 1,3-diketonate, a C₁-C₈ alkoxide, OH^-, ClO₄^-, By₄^-, PF₆^-, SbCl₆^-, AsCl₆^-, SbF₆^-, AsF₆^-_, a R^dSO₃^- wherein R^d is a chlorine of fluoride atom or a C₁-C₈ alkyl, aryl, fluoroalkyl or fluoroaryl group, or a BR^e₄^- wherein R^e is a phenyl group optionally substituted by one to five groups such as halide atoms and/or methyl and/or CF₃ groups.

[0057] According to any one of the above embodiments, said Y represents Cl^-, acetylacetonate, BF₄^-, PF₆^- or CF₃SO₃^-. In particular said Y represents Cl^-.

[0058] The examples of Y provided above are applicable for both compounds (1) and (2). Anyhow, as a person skilled in the art would recognise, the mono-anion present in the precursor (1) will be the same as that of the compound (2). In the case wherein Y is a basic anion having a pK_a comprised within the pk_a range disclosed above for the base, said Y may also serve as at least part of the base added into the catalytic system.

[0059] Non-limiting examples of precursors of formula (1) are the following: acetylacetonato(1,5-cyclooctadiene)rhodium(I), bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate, bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate, bis(1,5-cyclooctadiene)rhodium(I) tetrakis[bis(3,5-trifluoromethyl)phenyl]borate, bis(norbornadiene)rhodium(I) tetrafluoroborate, chlorobis(1,5-cyclooctadiene)rhodium(I) dimer, chloronorbornadienerhodium(I) dimer, di-µ-methoxobis(1,5-cyclooctadiene)dirhodium(I) or hydroxy(1,5-cyclooctadiene)rhodium(I) dimer.

[0060] According to any one of the above embodiments, L2 can be a compound of formula

        (R^b)₂P-Q-P(R^b)₂     (A)

wherein each R^b, taken separately, represents a C_6-10 aromatic group optionally substituted or a cyclohexyl group optionally substituted, or the two R^b bonded to the same P atom, taken together, represent a 2,2'-oxydiphenyl optionally substituted; and Q represents a C₁₀-C₁₆ metallocenediyl optionally substituted or a group of formula

• a)
  
  wherein each R^d represents a hydrogen atom or a C_1-8 alkyl group, and X represents an oxygen or sulfur atom or a C(R¹⁰)₂, Si(R¹¹)₂ or NR¹⁰ group, in which R¹⁰ is a hydrogen atom or a R¹¹ group, R¹¹ representing a C_1-4 linear or branched alkyl group, preferably methyl; or
• b)
  
  in the form of any one of its enantiomers, and wherein m is 0 or 1, M represents Fe or Ru, and R^a represents a hydrogen atom or a C_1-4 alkyl group;

and the wavy lines indicate the position of the bond between said Q group and the rest of the compound (A).

[0061] According to any one of the above embodiments, Q represents a 1,1'-ferrocenediyl optionally substituted or a group of formula

• a)
  
  wherein each R^d represents a hydrogen atom or a C_1-4 alkyl group, and X represents a C(R¹⁰)₂, Si(R¹¹)₂ or NR¹⁰ group, in which R¹⁰ is a hydrogen atom or a R¹¹ group, R¹¹ representing a C_1-4 linear or branched alkyl group, preferably methyl; or
• b)
  
  in the form of any one of its enantiomers;

the wavy lines indicate the position of the bond between said Q group and the rest of the compound (A).

[0062] According to any one of the above embodiments, in the definition of Q the metallocenediyl is a ferrocenediyl and in particular a 1,1'-diyl group. In formula (II), in particular M is Fe.

[0063] According to any one of the above embodiments, each R^b represents a C_6-10 aromatic group optionally substituted or a cyclohexyl group optionally substituted.

[0064] According to any one of the above embodiments, by "aromatic group or ring" it is meant a phenyl or naphthyl group, and in particular a phenyl group.

[0065] According to any one of the above embodiments, each R^b represents a phenyl group, a cyclohexyl group, a 3,5-dimethyl-phenyl, a 3,5-di(CF₃)-phenyl, a 3,5-dimethyl-4-methoxy-phenyl group.

[0066] According to any one of the above embodiments, the R^d represents a hydrogen atom.

[0067] According to any one of the above embodiments, X represents a CMe₂, SiMe₂, NH or NMe group.

[0068] According to any one of the above embodiments, L2 has a natural bite-angle comprised between 97° and 120°.

[0069] According to any one of the above embodiments, non-limiting examples of possible substituents of R^b are one, two, three or four groups selected amongst the halogen atoms, or C_1-10 alkoxy, alkyl, alkenyl, or perhalo-hydrocarbon group. The expression "perhalo-hydrocarbon" has here the usual meaning in the art, e.g. a group such as CF₃ for instance. In particular said substituents are one or two halogen atoms, such as F or Cl, or C_1-4 alkoxy or alkyl groups, or CF₃ groups.

[0070] According to any one of the above embodiments, non-limiting examples of possible substituents of the metallocenediyl or 1,1'-ferrocenediyl group are one or two C_1-4 alkyl groups or a CR^d'PHN(R^d")₂ group, wherein R^d' or R^d" are a hydrogen atom or a C_1-4 alkyl group and Ph is a phenyl group optionally substituted as indicated above for R^c. In particular, said substituents are one methyl or one CH(C₆H₅)N(Me)₂ group.

[0071] According to any one of the above embodiments, said R^b, metallocenediyl or 1,1'-ferrocenediyl groups, one by one or all together, are non substituted.

[0072] According to any one of the above embodiments, the ligand of formula (A) can be in a racemic or optically active form.

[0073] As non limiting examples of L2 ligands, one can cite the following ones:



wherein Cy represents a cyclohexyl substituted by one or two C_1-4 alkyl groups, Ph
represents a phenyl group optionally substituted by one or two C_1-4 alkyl groups; said compounds being in an optically active form or in a racemic form, if applicable.

[0074] The ligands (A) are all known in the prior art and can be obtained by applying standard general methods which are well known in the state of the art and by the person skilled in the art, e.g. see R. P. J. Bronger, P. C. J. Kamer, P. W. N. M. van Leeuwen, Organometallics 2003, 22, 5358 or R. P. J. Bronger, J. P. Bermon, J. Herwig, P. C. J. Kamer, P. W. N. M. van Leeuwen, Adv. Synth. Catal. 2004, 346, 789 or M. Kranenburg, Y. E. M. van der Burgt, P. C. J. Kamer, P. W. N. M. van Leeuwen, K. Goubitz, J. Fraanje Organometallics 1985, 14, 3081 or P. Dierkes, P. W. N. M. van Leeuwen J. Chem. Soc., Dalton Trans. 1999, 1519. Some of said ligands are even commercially available.

[0075] The Rh complex of the invention can be added into the reaction medium of the invention's process in a large range of concentrations. As non-limiting examples, one can cite as complex concentration amounts of complex being greater than 10 ppm, preferably greater than 100 ppm, more preferably greater than 1000 ppm, but less than 50000 ppm, preferably less than 10000 ppm, relative to the amount of substrate. It goes without saying that the optimum concentration of complex will depend, as the person skilled in the art knows, on the nature of the latter, on the nature of the substrate, of the solvent and on the pressure of H₂ used during the process, as well as the desired time of reaction.

[0076] Useful quantities of base, added to the reaction mixture, may be comprised in a relatively large range. One can cite, as non-limiting examples, amounts of base being greater than 0.1, preferably greater than 1, more preferably greater than 5, but less than 1000, preferably less than 500 molar equivalents, relative to the complex (e.g. base/com = up to 10000).

[0077] The complex (1) of the invention can be obtained by applying standard general methods which are well known in the state of the art and by the person skilled in the art. Some of said ligands are even commercially available.

Examples

[0078] The invention will now be described in further detail by way of the following examples, wherein the temperatures are indicated in degrees centigrade and the abbreviations have the usual meaning in the art.

[0079] All the procedures described hereafter have been carried out under an inert atmosphere unless stated otherwise. Hydrogenations were carried out in a stainless steel autoclave otherwise indicated. H₂ gas (99.99990%) was used as received. All substrates and solvents were distilled from appropriate drying agents under Ar. NMR spectra were recorded on a Bruker AM-400 (¹H at 400.1 MHz, ¹³C at 100.6 MHz, and ³¹P at 161.9 MHz) spectrometer and normally measured at 300 K, in CDCl₃ unless indicated otherwise. Chemical shifts are listed in ppm.

Example 1

Catalytic hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal using various invention rhodium complexes (formation in situ, from [Rh(COD)Cl]₂ precursor with diphosphines ligands (La-Ld))

A typical experimental procedure is as follows:

[0080] In a glove box under argon, a glass vial equipped with a teflon-coated magnetic stirring bar was charged with the Rh precursor (e.g. [Rh(COD)Cl]₂, 0.005 mmol, 1 mol%), the diphosphine ligand (0.005 mmol, 1 mol%, see Table 1), the optional base (e.g. KOAc, 0.05 mmol, 10 mol%) and CH₂Cl₂ (1ml). The solution was then stirred for 1 hour at room temperature. Then a solution of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (0.5 mmol) in CH₂Cl₂ (1ml) was added. The vial was then placed in a 75ml stainless steel autoclave, the autoclave was closed and purged with H₂ (6 x 20 bar) and pressurized with H₂ (50 bar) and the solution was stirred at room temperature. After 1 hour, the autoclave was vented and a sample was taken, diluted with MTBE, and the solution was then filtered over a plug of celite 560 and analysed by GC (DB-Wax).
Under these conditions several diphosphines ligands (Table 1) were tested, as reported in Table 2.

Table 1: Structure of diphosphine ligands (La-Ld) used

Structure	Structure	Structure
La		Lc
n.b.a.= 95°	Lb	n.b.a.= 111°

Structure	Structure	Structure
Ld
n.b.a.= 114°

wherein Ph is a C₆H₅ group; n.b.a. means the natural bite angle.

Table 2: Hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into (E)-4-methyl-5-(p-tolyl)pent-4-enal with diphosphine (PP, La-Lc), in presence of a base

N°	PP	Rhodium precursor	Com / Base	Base	Time [min]	Conv. %	Sel. %
1	La	[Rh(COD)Cl]2	10000 / 100000	KOAc	60	62	79
2	Lb	[Rh(COD)Cl]2	10000/100000	KOAc	60	84	42
3	Lc	[Rh(COD)Cl]2	10000 / 100000	KOAc	60	100	85

Wherein COD is 1,5-cyclooctadiene and KOAc is potassium acetate. Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into any other product (including deconjugated enal, the saturated aldehyde and the alcohol) after the indicated time. Reaction conditions: H2 gas (50 bar), 25°C, CH2Cl2 (c.a. 0.25 M). Sel. = selectivity (in (%), analysed by GC) and calculated as [100 x (E)-4-methyl-5-(p-tolyl)pent-4-enal]/[(E)-4-methyl-5-(p-tolyl)pent-4-enal + of other product].

Example 2

Catalytic hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal using [Rh(COD)(Ld)][Cl] as invention rhodium complexes (use of various bases)

A typical experimental procedure is as follows :

[0081] In a glove box under argon, a glass vial equipped with a teflon-coated magnetic stirring bar was charged with [Rh(COD)(Ld)][Cl] (0.02 mmol, 1 mol%), the base (0.02 mmol, 1 mol%) and toluene (1 ml). The solution was then stirred for 1 hour at room temperature. Then a solution of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (2 mmol) in toluene (1ml) was added. The vial was then placed in a 75ml stainless steel autoclave, the autoclave was closed and purged with H₂ (6 x 20 bar) and pressurized with H₂ (30 bar) and the solution was stirred at room temperature. After 90 min, the autoclave was vented and a sample was taken, diluted with MTBE, and the solution was then filtered over a plug of celite 560 and analysed by GC (DB-Wax).
Under these conditions several basic additive were tested, as reported in Table 3.

Table 3: Hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into (E)-4-methyl-5-(p-tolyl)pent-4-enal with [Rh(COD)(Ld)][Cl] and a base

N°	Com / Base	Base	Conv. %	Sel. %
1	10000 / ----	none	12	92
2	10000 / 10000	KOAc	100	57
3	10000 / 10000	NaOC(O)Ph	100	85
4	10000 / 10000	KOC(O)Ph	100	57
5	10000 / 10000	Na(acac)	100	83
6	10000 / 10000	Na(tBu-acac)	100	92
7	10000 / 10000	NaOPh	100	91
8	10000 / 10000	NaO(2,6-(tBu)2-4-Me)-C6H2	100	93
9	10000 / 10000	Cs2CO3	100	80

Wherein NaOAc is sodium acetate, KOAc is potassium acetate, NaOC(O)Ph is sodium benzoate, KOC(O)Ph is potassium benzoate, Na(acac) is sodium 4-oxopent-2-en-2-olate, Na(tBu-acac) is sodium 2,2,6,6-tetramethyl-5-oxohept-3-en-3-olate, NaOPh is sodium phenolate, NaO(2,6-(tBu)2-4-Me)-C6H2 is sodium 2,6-di-tert-butyl-4-methylphenolate. Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into any other product (including deconjugated enal, saturated aldehyde and alcohol) after the indicated time. Reaction conditions: H2 gas (30 bar), 25°C, toluene (c.a. 1 M), 90 min. Sel. = selectivity (in (%), analysed by GC) and calculated as [100 x (E)-4-methyl-5-(p-tolyl)pent-4-enal]/[(E)-4-methyl-5-(p-tolyl)pent-4-enal + of other product].

Example 3

Catalytic hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal using [Rh(COD)(Ld)][Cl] as invention rhodium complex under various S/C and S/B (substrate/complex and substrate/base) ratio

A typical experimental procedure is as follows :

[0082] In a glove box under argon, a stainless steel autoclave equipped with a teflon-coated magnetic stirring bar was charged with [Rh(COD)(Ld)][Cl] and the base. Then (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (10g 54 mmol) in toluene (12.5 ml) was added. The autoclave was closed and purged with H₂ (6 x 20 bar) and pressurized with H₂ (30 bar) and the solution was stirred at 60°C (bath temp.) for the indicated time. Then the autoclave was cooled to room temperature, vented and a sample was taken, diluted with MTBE, the solution was then filtered over a plug of celite 560 and analysed by GC (DB-Wax).
Under these conditions several S/C and S/B ratio were tested, as reported in Table 4.

Table 4: Hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into (E)-4-methyl-5-(p-tolyl)pent-4-enal with [Rh(COD)(Ld)][Cl] and a base

N°	Com / Base	Base	Time [h]	Conv. %	Sel. %
1	1000 / 1000	KOAc	2	99	93
2	100 / 1000	KOAc	4	98	100
3	50 / 500	KOAc	22	49	100
4	1000 / 1000	KOC(O)Ph	2	98	96
5	100 / 1000	KOC(O)Ph	4	99.5	100
6	50 / 500	KOC(O)Ph	22	99	100
7	1000 / 1000	Na(acac)	2	99.5	86
8	1000 / 1000	Na(tBu-acac)	2	99.5	90

Wherein NaOAc is sodium acetate, KOAc is potassium acetate, NaOC(O)Ph is sodium benzoate, KOC(O)Ph is potassium benzoate, Na(acac) is sodium 4-oxopent-2-en-2-olate, Na(tBu-acac) is sodium 2,2,6,6-tetramethyl-5-oxohept-3-en-3-olate. Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into any other product (including deconjugated enal and the aldehyde) after the indicated time. Reaction conditions: H2 gas (30 bar), 60°C, toluene (c.a. 4.3 M). Sel. = selectivity (in (%), analysed by GC) and calculated as [100 x (E)-4-methyl-5-(p-tolyl)pent-4-enal]/[(E)-4-methyl-5-(p-tolyl)pent-4-enal + of other product].

Example 4

Catalytic hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal using [Rh(COD)(Lc)][Cl] or [Rh(COD)(Ld)][Cl] as invention rhodium complex (use of various solvent)

A typical experimental procedure is as follows :

[0083] In a glove box under argon, a stainless steel autoclave equipped with a teflon-coated magnetic stirring bar was charged with [Rh(COD)(Lc)][Cl] (0.005 mmol, 0.1 mol%), potassium benzoate (0.05 mmol, 1 mol%), (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (5 mmol) and the appropriate solvent (5 ml). The autoclave was closed and purged with H₂ (6 x 20 bar) and pressurized with H₂ (50 bar) and the solution was stirred at room temperature. After 60 min, the autoclave was vented and a sample was taken, diluted with MTBE, and the solution was then filtered over a plug of celite 560 and analysed by GC (DB-Wax).
Under these conditions, several solvent were tested, as reported in Table 5.

Table 5: Hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into (E)-4-methyl-5-(p-tolyl)pent-4-enal with [Rh(COD)(Lc)][Cl] and potassium benzoate in various solvent

N°	Com / Base	Solvent	Conv. %	Sel. %
1	1000 / 10000	iPrOH	100	96
2	1000 / 10000	AcOEt	100	98
3	1000 / 10000	Acetone	100	98
4	1000 / 10000	THF	100	97
5	1000 / 10000	MTBE	100	98
6	1000 / 10000	toluene	100	97

Wherein iPrOH is iso-propanol, AcOEt is ethyl acetate, THF is tetrahydrofuran, MTBE is methyl-tert-butyl ether. Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into any other product (including deconjugated enal and the aldehyde) after the indicated time. Reaction conditions: H2 gas (50 bar), 25°C, solvent (1 M), 60 min. Sel. = selectivity (in (%), analysed by GC) and calculated as [100 x (E)-4-methyl-5-(p-tolyl)pent-4-enal]/[(E)-4-methyl-5-(p-tolyl)pent-4-enal + of other product]. [Rh(COD)(Ld)][Cl] was also tested using the same protocol, as reported in Table 6.

Table 6: Hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into (E)-4-methyl-5-(p-tolyl)pent-4-enal with [Rh(COD)(Ld)][Cl] and potassium benzoate in various solvent

N°	Com / Base	Solvent	Conv. %	Sel. %
1	5000 / 50000	iPrOH	99	96
2	5000 / 50000	AcOEt	100	92
3	5000 / 50000	Acetone	100	90
4	5000 / 50000	THF	100	93
5	5000 / 50000	MTBE	100	95

Wherein iPrOH is iso-propanol, AcOEt is ethyl acetate, THF is tetrahydrofuran, MTBE is methyl-tert-butyl ether. Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into any other product (including deconjugated enal and the aldehyde) after the indicated time. Reaction conditions: H2 gas (10 bar), 25°C, solvent (0.5 M), 120 min. Sel. = selectivity (in (%), analysed by GC) and calculated as [100 x (E)-4-methyl-5-(p-tolyl)pent-4-enal]/[(E)-4-methyl-5-(p-tolyl)pent-4-enal + of other product].

Example 5

Catalytic hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal using various invention rhodium complexes with potassium benzoate as a base in EtOH

[0084] Various complexes were also tested using the same protocol as described in Example 4, as reported in Table 7.

Table 7: Hydrogenation of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into (E)-4-methyl-5-(p-tolyl)pent-4-enal with various rhodium complexes and potassium benzoate in ethanol

N°	Com / Base	Rhodium complexes	Conv. %	Sel. %
1	1000 / 10000	[Rh(COD)(Lc)][Cl]	100	89
2	1000 / 10000	[Rh(NBD)(Lc)] [Cl]	100	93
3	1000 / 10000	[Rh(COD)(Lc)][BF4]	100	93
4	1000 / 10000	[Rh(COD)(Lc)][TfO]*	100	91

Wherein COD is 1,5-cyclooctadiene, NBD is norbornadiene, BF4 is tetrafluoroborate, TfO is trifluoromethanesulfonate. Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into any other product (including deconjugated enal and the aldehyde) after the indicated time. Reaction conditions: H2 gas (20 bar), 60°C, EtOH (1 M), 120 min. Sel. = selectivity (in (%), analysed by GC) and calculated as [100 x (E)-4-methyl-5-(p-tolyl)pent-4-enal]/[(E)-4-methyl-5-(p-tolyl)pent-4-enal + of other product]. * Generated in-situ from [Rh(COD)2][TfO].

Example 6

Catalytic hydrogenation of various dienal using [Rh(COD)(Ld)][Cl] as invention rhodium complex

A typical experimental procedure is as follows :

[0085] In a glove box under argon, a stainless steel autoclave equipped with a teflon-coated magnetic stirring bar was charged with [Rh(COD)(Ld)][Cl] and potassium benzoate. Then a solution of the appropriate substrate (2.5 mmoles) in a solvent (10 mL) was added. The autoclave was closed and purged with H₂ (6 x 20 bar) and pressurized with H₂ (20-25 bar) and the solution was stirred at the indicated temperature for the indicated time. Then the autoclave was cooled to room temperature, vented and a sample was taken, diluted with MTBE, the solution was then filtered over a plug of celite 560 and analysed by GC (DB-Wax).
Under these conditions several dienals (Table 8) were tested, as reported in Table 9.

Table 8: Structure of dienals (Da-Dt) used

Structure	Structure	Structure
Structure	Structure	Structure
Structure	Structure	Structure
Structure	Structure	Structure
Structure	Structure	Structure
Structure	Structure	Structure
Structure	Structure	Structure

Table 9: Hydrogenation of various dienals (Da-Dt) into their corresponding nonconjugated enal with [Rh(COD)(Ld)][Cl] and a base

N°	D	Com / Base	Base	Solvent	T [°C]	Time [h]	Conv. %	Sel. %
1*	Da	10000 / 50000	KOAc	CH2Cl2	25	1	100	66
2*	Da	10000 / 50000	KOC(O)Ph	CH2Cl2	25	1	100	92
3*	Da	2000 / 50000	KOC(O)Ph	CH2Cl2	25	7	96	85
4*	Db	2000 / 50000	KOC(O)Ph	CH2Cl2	25	7	100	98
5*	Dc	2000 / 50000	KOC(O)Ph	CH2Cl2	25	7	100	98
6*	Dd	2000 / 50000	KOC(O)Ph	CH2Cl2	25	7	100	40
7*	De	2000 / 50000	KOC(O)Ph	CH2Cl2	25	7	100	96
8*	Df	1000 / 10000	KOAc	toluene	25	17	96	91
9**	Dg	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	99
10**	Dh	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	99
11**	Di	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	84
12***	Dj	2000 / 20000	KOC(O)Ph	EtOH	50	5	100	93
13***	Dk	1000 / 10000	KOC(O)Ph	EtOH	50	5	100	88
14***	Dl	1000 / 10000	KOC(O)Ph	EtOH	50	5	100	99
15**	Dm	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	94
16**	Dn	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	96
17**	Do	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	98
18**	Dp	1000 / 10000	KOC(O)Ph	EtOH	60	2	99	93
19**	Dq	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	99
20**	Dr	1000 / 10000	KOC(O)Ph	EtOH	60	4	100	97
21**	Ds	1000 / 10000	KOC(O)Ph	EtOH	60	5	99	99
22**	Dt	1000 / 10000	KOC(O)Ph	EtOH	60	5	100	68

Wherein KOAc is potassium acetate, KOC(O)Ph is potassium benzoate. Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of the starting dienal into any other product (including deconjugated enal, the saturated aldehyde or the alcohol) after the indicated time. * Reaction conditions: H2 gas (25 bar), 25°C, CH2Cl2 (c.a. 0.25-1 M). ** Reaction conditions: H2 gas (20 bar), 60°C, EtOH (c.a. 0.5 M). *** Reaction conditions: H2 gas (20 bar), 50°C, EtOH (c.a. 0.5 M). Sel. = selectivity (in (%), analysed by GC) and calculated as [100 x 4-enal]/[4-enal + sum of other products].

Comparative Example 1

Comparison of catalytic reduction of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (S1) and (E)-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one (S2) using various reduction methods

A typical experimental procedure for the reduction under H₂ gas is as follows:

[0086] In a glove box under argon, a stainless steel autoclave equipped with a teflon-coated magnetic stirring bar was charged with the desired catalyst, the optional basic additive (0.1 mmol, 1 mol%), (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (10 mmol) and toluene (10 ml). The autoclave was closed and purged with H₂ (6 x 20 bar) and pressurized with H₂ at the desired pressure and the solution was stirred at the desired temperature. After the indicated time, the autoclave was vented, a sample was taken, diluted with MTBE, and the solution was then filtered over a plug of celite 560 and analysed by GC (DB-Wax).

A typical experimental procedure for the reduction with Et₃SiH is as follows:

[0087] In a glove box under argon, a Schlenck flask equipped with a teflon-coated magnetic stirring bar was charged with the desired catalyst, (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (10 mmol) and toluene (10 ml). Then Et₃SiH (11 mmol) was added with a syringe and the solution stirred at 50°C. After the indicated time, the solution was cooled to RT, a sample was taken, diluted with MTBE, analysed by GC (DB-1).
Under these conditions different reduction conditions were tested, as reported in Table 10.

Table 10: Reduction of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal (S1) and (E)-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one (S2) with various reduction methods

N°	Substrate	Com / Base	Catalyst	Hydride source	Conv. %	Sel. %
Present invention substrate, catalysts and conditions
1	S1	1000/ 10000	[Rh(COD)(Lc)] [C1] KOC(O)Ph	H2 (20 bar)*	100	94
5	S1	1000/10000	[Rh(COD)(Lc)] [C1] KOC(O)Ph	H2 (50 bar)***	100	97

Present invention substrate and prior art1) catalysts and conditions
4	S1	1000/0	[Rh(PPh3)3Cl]	Et3SiH (1 eq.)**	0	-

Present invention substrate and conditions and prior art1) catalysts
2	S1	1000/0	[Rh(PPh3)3Cl]	H2 (20 bar)*	6	-
3	S1	1000/10000	[Rh(PPh3)3Cl] KOC(O)Ph	H2 (20 bar)*	11	82

Present invention catalysts and conditions and prior art1) substrate
6	S2	1000/10000	[Rh(COD)(Lc)][Cl] KOC(O)Ph	H2 (50 bar)***	6	-

Com/Base: molar ratio in ppm relative to the substrate. Conv. = conversion (in (%), analysed by GC) of (2E,4E)-4-methyl-5-(p-tolyl)penta-2,4-dienal into any other product (including deconjugated enal and the aldehyde) after the indicated time. 1) Ojima et al. in Organomet. 1982, 1390 * Reaction conditions: 50°C, toluene (1 M), 120 min. ** Reaction conditions: 50°C, toluene (1 M), 18h. *** Reaction conditions: 25°C, toluene (1 M), 60 min. Sel. = selectivity (in (%), analyzed by GC) and calculated as [100 x (E)-4-methyl-5-(p-tolyl)pent-4-enal]/[(E)-4-methyl-5-(p-tolyl)pent-4-enal + of other product].

[0088] As can be noticed, modifying according to the prior art any characteristics of the present invention does not allow to obtain the desired product in useful yields.

Claims

1. A process for the reduction by hydrogenation, using molecular H₂, of a C₆-C₂₀ conjugated dienal of formula

wherein, when taken separately, each of R¹, R², R³, R⁴ and R⁵ represents, independently of each other, a hydrogen atom, a phenyl group optionally substituted or a C_1-8 alkyl, alkenyl, cycloalkyl or cycloalkenyl group optionally substituted, provided that at least one of said R¹, R², R³, R⁴ and R is not a hydrogen atom; R¹ and R² or R² and R³ or R³ and R⁴, when taken together, represent a C_3-4 alkadienyl or alkenediyl group optionally substituted; R¹ and R³ or R² and R⁵, when taken together, represent a C_2-3 alkadienyl or alkenediyl group optionally substituted; R⁴ and R⁵, when taken together, represent a C_4-5 alkadienyl or alkenediyl group optionally substituted;
and the substituents of R¹ to R⁵ are one phenyl group or one, two or three COOR⁷, OR⁶ or R⁷ groups, in which R⁶ is a hydrogen atom or a R⁷ group, R⁷ representing a C_1-4 linear or branched alkyl or alkenyl group;
into a deconjugated enal of formula

wherein R¹ to R⁵ are defined as in formula (I);
said process being carried out in the presence of a catalytic system comprising:

- at least a base; and

- at least one Rh(I) complex obtainable by reacting together :

- a C₃₄-C₆₀ bidentate diphosphine ligand (L2) having a natural bite-angle comprised between 93° and 130°; and

- a suitable Rh(I) precursor of formula

        [Rh(L)(S)_vY_r](Y)_1-r     (1)

or

        [Rh(L)₂](Y)     (1')

wherein r is 0 or 1, v is 0, 1 or 2;
L represents a C_5-14 hydrocarbon diene;
S represents a coordinated molecule of a polar organic solvent or water; and
Y represents a mono-anion.

2. A process according to claim 1, characterized in that said compound of formula (I) and (II) is a C₆-C₁₅ compound wherein, when taken separately, each of R¹, R², R³, R⁴ and R⁵ represents, independently of each other, a hydrogen atom, a phenyl group optionally substituted or a C_1-4 alkyl or cycloalkyl group optionally substituted, provided that at least one of said R¹, R², R³, R⁴ and R⁵ is not a hydrogen atom; R³ and R⁴, when taken together, represent a C_3-4 alkadienyl group optionally substituted; R⁴ and R⁵, when taken together, represent a C_4-5 alkadienyl group optionally substituted.

3. A process according to claim 1, characterized in that said compound of formula (I) and (II) is a compound wherein R¹, R² represent each a hydrogen atom, R³, R⁴, R⁵ represent each a hydrogen atom or a methyl or ethyl group or a cyclohexyl or phenyl group optionally substituted, provided that at least one of said R¹, R², R³, R⁴ and R⁵ is not an hydrogen atom; R³ and R⁴, when taken together, represent a C₄ alkadienyl group optionally substituted.

4. A process according to claim 1, characterized in that said base is an organic or inorganic base having preferentially a pK_a, of the protonated base, comprised between about 2 and 12.

5. A process according to claim 1, characterized in that said base is : as inorganic base an alkaline or C_4-16 ammonium carbonate or bicarbonate, a basic alox, a siliconate, or an alkaline alkaline-earth or C_4-16 ammonium fluoride; as organic base an alkaline or C_4-16 ammonium C_2-10 carboxylate, or an alkaline or C_4-16 ammonium C_6-10 phenolate optionally substituted, an alkaline or C_4-16 ammonium C_5-15 1,3-diketonate, or a C_8-10 bicyclic amidine.

6. A process according to claim 1, characterized in that said base is a carbonate, or a fluoride, or a carboxylate such as an acetate or benzoate, or a C_5-15 1,3-diketonate such as an acetylacetonate or a 5-oxohept-3-en-3-olate, or a phenolate such as a phenolate or a naphtholate.

7. A process according to claim 1, characterized in that said base is sodium acetate, potassium acetate, sodium benzoate, potassium benzoate, sodium (Z)-4-oxopent-2-en-2-olate, sodium (Z)-2,2,6,6-tetramethyl-5-oxohept-3-en-3-olate, sodium phenolate, sodium 2,6-di-tert-butyl-4-methylphenolate, cesium carbonate.

8. A process according to claim 1, characterized in that said Rh(I) complex is a compound of formula

        [Rh(L2)(L)](Y)     (2)

wherein L2, L and Y have the same meaning as in claim 1.

9. A process according to claim 1 or 8, characterized in that said L represents a linear or branched C₅-C₁₄ hydrocarbon compound comprising two carbon-carbon double bonds or a cyclic C₇-C₁₄ hydrocarbon compound comprising two carbon-carbon double bonds.

10. A process according to claim 1 or 8, characterized in that said Y represents a halide, a C_5-15 1,3-diketonate, a C₁-C₈ alkoxide, OH^-, ClO₄^-, BF₄^-, PF₆^-, SbCl₆^-, AsCl₆^-, SbF₆^-, AsF₆^-, a R^dSO₃^- wherein R^d is a chlorine of fluoride atom or a C₁-C₈ alkyl, aryl, fluoroalkyl or fluoroaryl group, or a BR^e₄^- wherein R^e is a phenyl group optionally substituted by one to five groups such as halide atoms and/or methyl and/or CF₃ groups.

11. A process according to claim 1, characterized in that said S represents a C_4-7 ether, or a C_1-4 alcohol, or water or N,N-dimethylformamide.

12. A process according to claim 1 or 8, characterized in that said L2 is a compound of formula

        (R^b)₂P-Q-P(R^b)₂     (A)

wherein each R^b, taken separately, represents a C_6-10 aromatic group optionally substituted or a cyclohexyl group optionally substituted, or the two R^b bonded to the same P atom, taken together, represent a 2,2'-oxydiphenyl optionally substituted; and
Q represents a C₁₀-C₁₆ metallocenediyl optionally substituted or a group of formula

- a)

wherein each R^d represents a hydrogen atom or a C_1-8 alkyl group, and X represents an oxygen or sulfur atom or a C(R¹⁰)₂, Si(R¹¹)₂ or NR¹⁰ group, in which R¹⁰ is a hydrogen atom or a R¹¹ group, R¹¹ representing a C_1-4 linear or branched alkyl group, preferably methyl; or

- b)

in the form of any one of its enantiomers, and wherein m is 0 or 1, M represents Fe or Ru, and R^a represents a hydrogen atom or a C_1-4 a alkyl group;

and the wavy lines indicate the position of the bond between said Q group and the rest of the compound (A); and
the substituents of R^b are one, two, three or four groups selected amongst the halogen atoms, or C_1-10 alkoxy, alkyl, alkenyl, or perhalo-hydrocarbon group;
the possible substituents of the metallocenediyl are one C_1-4 alkyl group or a CR^d'PhN(^Rd")₂ group, wherein R^d' or R^d" are a hydrogen atom or a C_1-4 alkyl group and Ph is a phenyl group optionally substituted as indicated above for R^c.

13. A process according to claim 12, characterized in that said R^b represent each a C_6-10 aromatic group optionally substituted or a cyclohexyl group optionally substituted.

14. A process according to claim 12, characterized in that said Q represents a 1,1'-ferrocenediyl optionally substituted or a group of formula

- a)

wherein each R^d represents a hydrogen atom or a C_1-4 alkyl group, and X represents a C(R¹⁰)₂, Si(R¹¹)₂ or NR¹⁰ group, in which R¹⁰ is a hydrogen atom or a R¹¹ group, R¹¹ representing a C_1-4 linear or branched alkyl group, preferably methyl; or

- b)

in the form of any one of its enantiomers;

the wavy lines indicate the position of the bond between said Q group and the rest of the compound (A).

15. A process according to claim 12, characterized in that said L2 has a natural bite-angle comprised between 97° and 120°.

Ansprüche

1. Verfahren für die Reduktion durch Hydrierung unter Verwendung von molekularem H₂ von einem konjugierten C₆-C₂₀-Dienal der Formel

wobei, wenn gesondert genommen, jedes von R¹, R², R³, R⁴ und R⁵, unabhängig voneinander, ein Wasserstoffatom, eine Phenylgruppe, wahlweise substituiert, oder eine C_1-8-Alkyl-, -Alkenyl-, -Cycloalkyl- oder -Cycloalkenylgruppe, wahlweise substituiert, darstellt, mit der Maßgabe, dass mindestens eines von den R¹, R², R³, R⁴ und R⁵ nicht ein Wasserstoffatom ist; R¹ und R² oder R² und R³ oder R³ und R⁴, wenn zusammengenommen, eine C_3-4-Alkadienyl- oder -Alkendiylgruppe, wahlweise substituiert, darstellen; R¹ und R³ oder R² und R⁵, wenn zusammengenommen, eine C_2-3-Alkadienyl- oder -Alkendiylgruppe, wahlweise substituiert, darstellen; R⁴ und R⁵, wenn zusammengenommen, eine C_4-5-Alkadienyl- oder -Alkendiylgruppe, wahlweise substituiert, darstellen;
und die Substituenten von R¹ bis R⁵ eine Phenylgruppe oder eine, zwei oder drei COOR⁷-, OR⁶- oder R⁷-Gruppen sind, in welchen R⁶ ein Wasserstoffatom oder eine R⁷-Gruppe ist, wobei R⁷ eine lineare oder verzweigte C_1-4-Alkyl- oder - Alkenylgruppe darstellt;
zu einem dekonjugierten Enal der Formel

wobei R¹ bis R⁵ wie in Formel (I) definiert sind;
wobei das Verfahren in Gegenwart von einem katalytischen System ausgeführt wird, das umfasst:

- mindestens eine Base; und

- mindestens einen Rh(I)-Komplex, erhältlich durch miteinander Umsetzen von:

- einem zweizähnigen C₃₄-C₆₀-Diphosphinliganden (L2), aufweisend einen natürlichen Greifwinkel zwischen 93° und 130°; und

- einem geeigneten Rh(I)-Vorläufer der Formel

        [Rh(L)(S)_vY_r](Y)_1-r     (1)

oder

        [Rh(L)₂](Y)     (1')

wobei r 0 oder 1 ist, v 0, 1 oder 2 ist;
L ein C₅-₁₄-Kohlenwasserstoffdien darstellt;
S ein koordiniertes Molekül von einem polaren organischen Lösungsmittel oder Wasser darstellt; und
Y ein Monoanion darstellt.

2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Verbindung der Formel (I) und (II) eine C₆-C₁₅-Verbindung ist, wobei, wenn gesondert genommen, jedes von R¹, R², R³, R⁴ und R⁵, unabhängig voneinander, ein Wasserstoffatom, eine Phenylgruppe, wahlweise substituiert, oder eine C_1-4-Alkyl- oder - Cycloalkylgruppe, wahlweise substituiert, darstellt, mit der Maßgabe, dass mindestens eines von den R¹, R², R³, R⁴ und R⁵ nicht ein Wasserstoffatom ist; R³ und R⁴, wenn zusammengenommen, eine C_3-4-Alkadienylgruppe, wahlweise substituiert, darstellen; R⁴ und R⁵, wenn zusammengenommen, eine C_4-5-Alkadienylgruppe, wahlweise substituiert, darstellen.

3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Verbindung der Formel (I) und (II) eine Verbindung ist, wobei R¹, R² jeweils ein Wasserstoffatom darstellen, R³, R⁴, R⁵ jeweils ein Wasserstoffatom oder eine Methyl- oder Ethylgruppe oder eine Cyclohexyl- oder Phenylgruppe, wahlweise substituiert, darstellen, mit der Maßgabe, dass mindestens eines von den R¹, R², R³, R⁴ und R⁵ nicht ein Wasserstoffatom ist; R³ und R⁴, wenn zusammengenommen, eine C₄-Alkadienylgruppe, wahlweise substituiert, darstellen.

4. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Base eine organische oder anorganische Base, aufweisend vorzugsweise einen pK_a der protonierten Base zwischen etwa 2 und 12, ist.

5. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Base ist:

als anorganische Base ein Alkali- oder C_4-16-Ammoniumcarbonat oder -bicarbonat, ein basisches Alox, ein Siliconat oder ein Alkali-Erdalkali- oder C_4-16-Ammoniumfluorid; als organische Base ein Alkali- oder C_4-16-Ammonium-C_2-10-carboxylat, oder ein Alkali- oder C_4-16-Amonium-C_6-10-phenolat, wahlweise substituiert, ein Alkali- oder C_4-16-Ammonium-C_5-15-1,3-diketonat, oder ein bicyclisches C_8-10-Amidin.

6. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Base ein Carbonat oder ein Fluorid oder ein Carboxylat wie beispielsweise ein Acetat oder Benzoat, oder ein C_5-15-1,3-Diketonat wie beispielsweise ein Acetylacetonat oder ein 5-Oxohept-3-en-3-olat oder ein Phenolat wie beispielsweise ein Phenolat oder ein Naphtholat ist.

7. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die Base Natriumacetat, Kaliumacetat, Natriumbenzoat, Kaliumbenzoat, Natrium-(Z)-4-oxopent-2-en-2-olat, Natrium-(Z)-2,2,6,6-tetramethyl-5-oxohept-3-en-3-olat, Natriumphenolat, Natrium-2,6-di-tert-butyl-4-methylphenolat, Cäsiumcarbonat ist.

8. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass der Rh(I)-Komplex eine Verbindung der Formel

        [Rh(L2)(L)](Y)     (2)

ist, wobei L2, L und Y die gleiche Bedeutung wie in Anspruch 1 haben.

9. Verfahren gemäß Anspruch 1 oder 8, dadurch gekennzeichnet, dass das L eine lineare oder verzweigte C₅-C₁₄-Kohlenwasserstoffverbindung, umfassend zwei Kohlenstoff-Kohlenstoff-Doppelbindungen, oder eine cyclische C₇-C₁₄-Kohlenwasserstoffverbindung, umfassend zwei Kohlenstoff-Kohlenstoff-Doppelbindungen, darstellt.

10. Verfahren gemäß Anspruch 1 oder 8, dadurch gekennzeichnet, dass das Y ein Halogenid, ein C_5-15-1,3-Diketonat, ein C₁-C₈-Alkoxid, OH^-, ClO₄^-, BF₄^-, PF₆^-, SbCl₆^-, AsCl₆^-, SbF₆^-, AsF₆^-, ein R^dSO₃^-, wobei R^d ein Chlor- oder Fluoridatom ist, oder eine C₁-C₈-Alkyl-, -Aryl-, -Fluoralkyl- oder -Fluorarylgruppe oder ein Bar^e₄^- darstellt, wobei R^e eine Phenylgruppe, wahlweise substituiert mit einer bis fünf Gruppen, wie beispielsweise Halogenidatomen und/oder Methyl- und/oder CF₃-Gruppen, ist.

11. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass das S einen C_4-7-Ether oder einen C_1-4-Alkohol oder Wasser oder N,N-Dimethylformamid darstellt.

12. Verfahren gemäß Anspruch 1 oder 8, dadurch gekennzeichnet, dass das L2 eine Verbindung der Formel

        (R^b)₂P-Q-P(R^b)₂     (A)

ist, wobei jedes R^b, gesondert genommen, eine aromatische C_6-10-Gruppe, wahlweise substituiert, oder eine Cyclohexylgruppe, wahlweise substituiert, darstellt, oder die zwei R^b, gebunden an das gleiche P-Atom, zusammengenommen ein 2,2'-Oxydiphenyl, wahlweise substituiert, darstellen; und
Q ein C₁₀-C₁₆-Metallocendiyl, wahlweise substituiert, oder eine Gruppe der Formel

- a)

darstellt, wobei jedes R^d ein Wasserstoffatom oder eine C_1-8-Alkylgruppe darstellt, und X ein Sauerstoff- oder Schwefelatom oder eine C(R¹⁰)₂-, Si(R¹¹)₂- oder NR¹⁰-Gruppe, in welcher R¹⁰ ein Wasserstoffatom oder eine R¹¹-Gruppe ist, darstellt, wobei R¹¹ eine lineare oder verzweigte C_1-4-Alkylgruppe, vorzugsweise Methyl, darstellt; oder

- b)

in der Form von einem ihrer Enantiomere, und wobei m 0 oder 1 ist, M Fe oder Ru darstellt und R^a ein Wasserstoffatom oder eine C_1-4-Alkylgruppe darstellt;

und die Wellenlinien die Position der Bindung zwischen der Q-Gruppe und dem Rest der Verbindung (A) anzeigen; und
die Substituenten von R^b eine, zwei, drei oder vier Gruppen, ausgewählt unter den Halogenatomen, oder eine C_1-10-Alkoxy-, -Alkyl-, -Alkenyl- oder Perhalogenkohlenwasserstoffgruppe sind;
die möglichen Substituenten des Metallocendiyls eine C_1-4-Alkylgruppe oder eine CR^d'PHN(R^d")₂-Gruppe sind, wobei R^d' order R^d" ein Wasserstoffatom oder eine C_1-4-Alkylgruppe sind und Ph eine Phenylgruppe, wahlweise substituiert, wie vorstehend für R^c angezeigt, ist.

13. Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass das R^b jeweils eine aromatische C_6-10-Gruppe, wahlweise substituiert, oder eine Cyclohexylgruppe, wahlweise substituiert, darstellt.

14. Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass das Q ein 1,1'-Ferrocendiyl, wahlweise substituiert, oder eine Gruppe der Formel

- a)

darstellt, wobei jedes R^d ein Wasserstoffatom oder eine C_1-4-Alkylgruppe darstellt, und X eine C(R10)₂-, Si(R¹¹)₂- oder NR¹⁰-Gruppe darstellt, in welcher R¹⁰ ein Wasserstoffatom oder eine R¹¹-Gruppe ist, wobei R¹¹ eine lineare oder verzweigte C_1-4-Alkylgruppe, vorzugsweise Methyl, darstellt; oder

- b)

in der Form von einem ihrer Enantiomere;

die Wellenlinien die Position der Bindung zwischen der Q-Gruppe und dem Rest der Verbindung (A) anzeigen.

15. Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass das L2 einen natürlichen Greifwinkel zwischen 97° und 120° hat.

Revendications

1. Procédé de réduction par hydrogénation, au moyen de H₂ moléculaire, d'un diénal conjugué en C₆-C₂₀ de formule

dans lequel, lorsqu'ils sont pris séparément, chacun des R¹, R², R³, R⁴ et R⁵ représente, indépendamment des autres, un atome d'hydrogène, un groupe phényle éventuellement substitué ou un groupe alkyle, alcényle, cycloalkyle ou cycloalcényle en C_1-8 éventuellement substitué, sous réserve qu'au moins un desdits R¹, R², R³, R⁴ et R⁵ ne soit pas un atome d'hydrogène; R¹ et R² ou R² et R³ ou R³ et R⁴, lorsqu'ils sont pris ensemble, représentent un groupe alcadiényle ou alcènediyle en C_3-4 éventuellement substitué; R¹ et R³ ou R² et R⁵ lorsqu'ils sont pris ensemble, représentent un groupe alcadiényle ou alcènediyle en C_2-3 éventuellement substitué; R⁴ et R⁵ lorsqu'ils sont pris ensemble, représentent un groupe alcadiényle ou alcènediyle en C_4-5 éventuellement substitué;
et les substituants de R¹ à R⁵ sont un groupe phényle ou un, deux ou trois groupes COOR⁷, OR⁶ ou R⁷, dans lesquels R⁶ est un atome d'hydrogène ou un groupe R⁷ R⁷ représentant un groupe alkyle ou alcényle linéaire ou ramifié en C_1-4;
pour donner un énal déconjugué de formule

dans lequel les R¹ à R⁵ sont définis comme dans la formule (I);
ledit procédé étant effectué en présence d'un système catalytique comprenant:

- au moins une base; et

- au moins un complexe de Rh(I), pouvant être obtenu en faisant réagir ensemble:

- un ligand diphosphine bidenté en C₃₄-C₆₀ (L2) ayant un angle de morsure naturel compris entre 93° et 130°; et

- un précurseur de Rh(I) approprié de formule

        [Rh(L)(S)_vY_r](Y)_1-r,     (1)

ou

        [Rh(L)₂](Y)     (1')

où r vaut 0 ou 1, v vaut 0, 1 ou 2;
L représente un diène hydrocarboné en C_5-14;
S représente une molécule coordinée de solvant organique polaire ou d'eau; et
Y représente un mono-anion.

2. Procédé selon la revendication 1, caractérisé en ce que ledit composé de formule (I) et (II) est un composé en C₆-C₁₅ dans lequel, lorsqu'ils sont pris séparément, chacun des R¹, R², R³, R⁴ et R⁵ représente, indépendamment des autres, un atome d'hydrogène, un groupe phényle éventuellement substitué ou un groupe alkyle ou cycloalkyle en C_1-4 éventuellement substitué, sous réserve qu'au moins un desdits R¹, R², R³, R⁴ et R⁵ ne soit pas un atome d'hydrogène; R³ et R⁴, lorsqu'ils sont pris ensemble, représentent un groupe alcadiényle en C_3-4 éventuellement substitué; R⁴ et R⁵ lorsqu'ils sont pris ensemble, représentent un groupe alcadiényle en C_4-5 éventuellement substitué.

3. Procédé selon la revendication 1, caractérisé en ce que ledit composé de formule (I) et (II) est un composé dans lequel R¹, R² représentent chacun un atome d'hydrogène, R³, R⁴, R⁵ représentent chacun un atome d'hydrogène ou un groupe méthyle ou éthyle ou un groupe cyclohexyle ou phényle éventuellement substitué, sous réserve qu'au moins un desdits R¹, R², R³, R⁴ et R⁵ ne soit pas un atome d'hydrogène; R³ et R⁴, lorsqu'ils sont pris ensemble, représentent un groupe alcadiényle en C₄ éventuellement substitué.

4. Procédé selon la revendication 1, caractérisé en ce que ladite base est une base organique ou inorganique ayant préférentiellement un pK_a, de la base protonée, compris entre environ 2 et 12.

5. Procédé selon la revendication 1, caractérisé en ce que ladite base est: en tant que base inorganique, un carbonate ou bicarbonate alcalin ou d'ammonium en C_4-16, un alox basique, un siliconate, ou un fluorure alcalin, alcalino-terreux ou d'ammonium en C_4-16; en tant que base organique, un carboxylate en C_2-10 alcalin ou d'ammonium en C_4-16, ou un phénolate en C_6-10 alcalin ou d'ammonium en C_4-16 éventuellement substitué, un 1,3-dicétonate en C_5-15 alcalin ou d'ammonium en C_4-16, ou une amidine bicyclique en C_8-10.

6. Procédé selon la revendication 1, caractérisé en ce que ladite base est un carbonate, ou un fluorure, ou un carboxylate tel qu'un acétate ou benzoate, ou un 1,3-dicétonate en C_5-15 tel qu'un acétylacétonate ou un 5-oxohept-3-én-3-olate, ou un phénolate tel qu'un phénolate ou naphtolate.

7. Procédé selon la revendication 1, caractérisé en ce que ladite base est de l'acétate de sodium, de l'acétate de potassium, du benzoate de sodium, du benzoate de potassium, du (Z)-4-oxopent-2-én-2-olate de sodium, du (Z)-2,2,6,6-tétraméthyl-5-oxohept-3-én-3-olate de sodium, du phénolate de sodium, du 2,6-di-tert-butyl-4-méthylphénolate de sodium, du carbonate de césium.

8. Procédé selon la revendication 1, caractérisé en ce que ledit complexe de Rh(I) est un composé de formule

        [Rh(L2)(L)](Y)     (2)

dans lequel L2, L et Y ont la même signification que dans la revendication 1.

9. Procédé selon la revendication 1 ou 8, caractérisé en ce que ledit L représente un composé hydrocarboné en C₅-C₁₄ linéaire ou ramifié comprenant deux doubles liaisons carbone-carbone ou un composé hydrocarboné en C₇-C₁₄ cyclique comprenant deux doubles liaisons carbone-carbone.

10. Procédé selon la revendication 1 ou 8, caractérisé en ce que ledit Y représente un halogénure, un 1,3-dicétonate en C_5-15, un alcoolate en C₁-C₈, OH^-, ClO₄^-, BF₄^-, PF₆^-, SbCl₆^-, AsCl₆^-, SbF₆^-, AsF₆^-, un R^dSO₃^- où R^d est un atome de chlore ou de fluor ou un groupe alkyle, aryle, fluoroalkyle ou fluoroaryle en C₁-C₈, ou un BR^e₄^- où R^e est un groupe phényle éventuellement substitué par un à cinq groupes tels que des atomes d'halogénure et/ou des groupes méthyle et/ou CF₃.

11. Procédé selon la revendication 1, caractérisé en ce que ledit S représente un éther en C_4-7, ou un alcool en C_1-4, ou de l'eau ou du N,N-diméthylformamide.

12. Procédé selon la revendication 1 ou 8, caractérisé en ce que ledit L2 est un composé de formule

        (R^b)₂P-Q-P(R^b)₂     (A)

dans lequel chaque R^b, pris séparément, représente un groupe aromatique en C_6-10 éventuellement substitué ou un groupe cyclohexyle éventuellement substitué, ou les deux R^b liés au même atome P, pris ensemble, représentent un 2,2'-oxydiphényle éventuellement substitué; et
Q représente un métallocènediyle en C₁₀-C₁₆ éventuellement substitué ou un groupe de formule

- a)

dans lequel chaque R^d représente un atome d'hydrogène ou un groupe alkyle en C_1-8, et X représente un atome d'oxygène ou de soufre ou un groupe C(R¹⁰)₂, Si(R¹¹)₂ ou NR¹⁰, dans lequel R¹⁰ est un atome d'hydrogène ou un groupe R¹¹, R¹¹ représentant un groupe alkyle linéaire ou ramifié en C_1-4, de préférence méthyle; ou

- b)

sous la forme de l'un quelconque de ses énantiomères, et où m vaut 0 ou 1, M représente Fe ou Ru, et R^a représente un atome d'hydrogène ou un groupe alkyle en C_1-4;

et les traits ondulés indiquent la position de la liaison entre ledit groupe Q et le reste du composé (A); et
les substituants de R^b sont un, deux, trois ou quatre groupes choisis parmi les atomes d'halogène, ou un groupe alcoxy, alkyle, alcényle, ou perhalogéno-hydrocarboné en C_1-10; les substituants possibles du métallocènediyle sont un groupe alkyle en C_1-4 ou un groupe CR^d' PHN(R^d")₂, où R^d' ou R^d" sont un atome d'hydrogène ou un groupe alkyle en C_1-4 et Ph est un groupe phényle éventuellement substitué comme indiqué ci-dessus pour R^c.

13. Procédé selon la revendication 12, caractérisé en ce que lesdits R^b représentent chacun un groupe aromatique en C_6-10 éventuellement substitué ou un groupe cyclohexyle éventuellement substitué.

14. Procédé selon la revendication 12, caractérisé en ce que ledit Q représente un 1,1'-ferrocènediyle éventuellement substitué ou un groupe de formule

- a)

dans lequel chaque R^d représente un atome d'hydrogène ou un groupe alkyle en C_1-4, et X représente un groupe C(R¹⁰)₂, Si(R¹¹)₂ ou NR¹⁰, dans lequel R¹⁰ est un atome d'hydrogène ou un groupe R¹¹, R¹¹ représentant un groupe alkyle linéaire ou ramifié en C_1-4, de préférence méthyle; ou

- b)

sous la forme de l'un quelconque de ses énantiomères;

les traits ondulés indiquent la position de la liaison entre ledit groupe Q et le reste du composé (A).

15. Procédé selon la revendication 12, caractérisé en ce que ledit L2 a un angle de morsure naturel compris entre 97° et 120°.